CN103803576B - A kind of low silica-alumina ratio ZSM-48 molecular sieve and preparation method thereof - Google Patents
A kind of low silica-alumina ratio ZSM-48 molecular sieve and preparation method thereof Download PDFInfo
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- CN103803576B CN103803576B CN201210440295.5A CN201210440295A CN103803576B CN 103803576 B CN103803576 B CN 103803576B CN 201210440295 A CN201210440295 A CN 201210440295A CN 103803576 B CN103803576 B CN 103803576B
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Abstract
The invention discloses a kind of low silica-alumina ratio ZSM-48 molecular sieve and preparation method thereof, this molecular sieve has following character: the mol ratio of silicon oxide and aluminum oxide is 25 ~ 50.This molecular sieve specific surface is 250 ~ 400m
2/ g, pore volume is 0.25 ~ 0.35cm
3/ g, mean pore size is 3 ~ 5nm.Preparation method comprises the steps: (1) mixes preparation feedback mixture by crystal seed S, template R, silicon source, aluminium source, sodium hydroxide and water; Reaction mixture has following composition, with oxide basis mol ratio: R/SiO
2=0.05 ~ 0.2; SiO
2/ Al
2o
3=30 ~ 50; Na
2o/SiO
2=0.06 ~ 0.1; H
2o/SiO
2=15 ~ 23; S/SiO
2mass ratio is 0.05 ~ 0.5; Wherein S is ZSM-48 molecular sieve, and R is 12-crown ether-4; (2) reaction mixture step (1) prepared is at 150 ~ 170 DEG C, and hydrothermal crystallizing 4 ~ 8 days, crystallization product after filtration, washing, dry and roasting obtain low silica-alumina ratio ZSM-48 molecular sieve.The ZSM-48 molecular sieve that the inventive method prepares has lower silica alumina ratio, has good application prospect in technical fields such as isomerization dewaxings.
Description
Technical field
The present invention relates to a kind of preparation method of molecular sieve, is exactly a kind of low silica-alumina ratio ZSM-48 molecular sieve and preparation method thereof specifically.
Background technology
Nineteen eighty-three, patent USP4397827 reported first has synthesized ZSM-48 molecular sieve.ZSM-48 molecular sieve is a kind of molecular sieve with ten-ring pore passage structure, and aperture is 0.53nm × 0.56nm.The ZSM-48 molecular sieve of pure silicon has the extensive concern that good selectivity of light olefin obtains people in the reaction of synthetic gas alkene.
At present, the research emphasis of ZSM-48 molecular sieve remains in its building-up process, the building-up process of this molecular sieve has following characteristics: the silica alumina ratio of the molecular sieve that (1) synthesizes is high, even if adopt expensive template, the silica alumina ratio of general synthesis of molecular sieve is also greater than 100; (2) if adopt the low template of cost, although reduce the cost of synthesis of molecular sieve, the silica alumina ratio of synthesis of molecular sieve can be very high, and need the crystallization time grown very much.The ZSM-48 molecular sieve of high silica alumina ratio, it is less that unit formula sieves the acid amount contained, and limits its widespread use in catalyzed reaction.Only having the ZSM-48 molecular sieve by improving synthetic method synthesizing low silicon aluminum ratio, improving the acid amount of unit formula sieve, the bottleneck of this restriction ZSM-48 molecular sieve widespread use can be broken through.
Within 1986, Mobil company has applied for one section of patent USP4585747 about ZSM-48 Zeolite synthesis, does template successfully synthesize ZSM-48 molecular sieve in this patent with unit molecule or bimolecular N-picoline.This building-up process will expect the ZSM-48 molecular sieve of pure phase, and the silicon oxide of building-up process gel and the feed ratio of aluminum oxide are all greater than 250, and generated time is all greater than 5 days.Within 1999, be that Mobil company has applied for that one section adopts quadrol to be the patent that template synthesizes ZSM-48 molecular sieve equally, in that patent, the feed ratio of synthesis of molecular sieve is reduced to 200 by investigator, and generated time also shortens to 65 hours, and more last section patent has had significantly to be improved.Until Mobil company in 2009 has just applied for two sections of patent USP7482300 about the synthesis of low silica-alumina ratio ZSM-48 molecular sieve and USP7625478 in succession.Although have employed the template chlorination Bistrium of price comparison costliness in that patent, its certain highly significant of effect, the silica alumina ratio that feeds intake is reduced to 100, and the silica alumina ratio of product reaches about 100, and crystallization time has also shortened to 48 hours.
Summary of the invention
In order to solve above-mentioned Problems existing, the invention provides a kind of low silica-alumina ratio ZSM-48 molecular sieve and preparation method thereof.Silica alumina ratio non-specifically described in the present invention points out the mol ratio being silicon oxide and aluminum oxide.
A kind of low silica-alumina ratio ZSM-48 of the present invention molecular sieve has following character: the mol ratio of silicon oxide and aluminum oxide is 25 ~ 50.Specific surface is 250 ~ 400m
2/ g, pore volume is 0.25 ~ 0.35cm
3/ g, mean pore size is 3 ~ 5nm.
The preparation method of a kind of low silica-alumina ratio ZSM-48 of the present invention molecular sieve, comprises the steps:
(1) crystal seed S, template R, silicon source, aluminium source, sodium hydroxide and water are mixed preparation feedback mixture;
(2) reaction mixture step (1) prepared is at 150 ~ 170 DEG C, and hydrothermal crystallizing 4 ~ 8 days, crystallization product after filtration, washing, dry and roasting obtain low silica-alumina ratio ZSM-48 molecular sieve.
In the inventive method, the mixture that step (1) is prepared has following composition, with oxide basis mol ratio: R/SiO
2=0.05 ~ 0.2; SiO
2/ Al
2o
3=30 ~ 50; Na
2o/SiO
2=0.06 ~ 0.1; H
2o/SiO
2=15 ~ 23; S/SiO
2mass ratio is 0.05 ~ 0.5; Wherein SiO
2do not comprise the silicon-dioxide in crystal seed S, S is ZSM-48 molecular sieve, and R is 12-crown ether-4.
In the inventive method, the temperature of preparation feedback mixture between 20 ~ 90 DEG C, preferably between 50 ~ 80 DEG C.
In the inventive method, crystal seed ZSM-48 molecular sieve is the sodium form molecular sieve of roasting or the sodium form molecular sieve of non-roasting, and the mol ratio of silicon oxide and aluminum oxide is between 30 ~ 150.
In the inventive method, template is 12-crown ether-4.
In the inventive method, silicon source is White Carbon black, and aluminium source is sodium aluminate.
In the inventive method, Yao Lv source, silicon source adds after dissolving completely.
The advantage of the inventive method is: by adding ZSM-48 molecular sieve as crystal seed, adopts 12-crown ether-4 to be template, has synthesized the ZSM-48 molecular sieve of the low silica-alumina ratio of pure phase.Compared with the ZSM-48 molecular sieve prepared with existing method, the silica alumina ratio of ZSM-48 zeolite product prepared by present method reduces greatly, improves the acid amount of molecular sieve.This molecular sieve has good application prospect in technical fields such as isomerization dewaxings.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the embodiment of the present invention 4 synthesis of molecular sieve.
Embodiment
Preparation process of the present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
(1) weighing sodium hydroxide and sodium aluminate (Al
2o
3, 43wt%; Na
2o, 38wt%) be dissolved in deionized water, then under bath temperature is 60 DEG C of conditions, template R(12-crown ether-4 is added while stirring, content >97%), stir after 0.5 hour, add white carbon black, stir and add crystal seed S after 1 hour, continue stirring and move on in airtight stainless steel cauldron after 2 hours.
(2) crystallization 6 days at 160 DEG C, the crystallization product obtained is ZSM-48 molecular sieve through XRD analysis, and concrete proportioning raw materials and product characteristics are in table 1.
Embodiment 2
(1) with embodiment 1 step (1).
(2) crystallization 8 days at 158 DEG C, the crystallization product obtained is ZSM-48 molecular sieve through XRD analysis, and concrete proportioning raw materials and product characteristics are in table 1.
Embodiment 3
(1) with embodiment 1 step (1), bath temperature is 80 DEG C.
(2) crystallization 5 days at 160 DEG C, the crystallization product obtained is ZSM-48 molecular sieve through XRD analysis, and concrete proportioning raw materials and product characteristics are in table 1.
Embodiment 4
(1) with embodiment 1 step (1).
(2) crystallization 4 days at 165 DEG C, the crystallization product obtained is ZSM-48 molecular sieve through XRD analysis, and concrete proportioning raw materials and product characteristics are in table 1.
Embodiment 5
(1) with embodiment 1 step (1), bath temperature is 50 DEG C.
(2) crystallization 8 days at 160 DEG C, the crystallization product obtained is ZSM-48 molecular sieve through XRD analysis, and concrete proportioning raw materials and product characteristics are in table 1.
Table 1 ZSM-48 Zeolite synthesis proportioning raw materials and product property.
| Each component relative proportion (mol ratio) | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| R/SiO 2 | 0.12 | 0.08 | 0.10 |
| SiO 2/Al 2O 3 | 35 | 48 | 45 |
| Na 2O/SiO 2 | 0.085 | 0.078 | 0.074 |
| H 2O/SiO 2 | 16.7 | 17.1 | 16.5 |
| Crystal seed S/SiO 2(mass ratio) | 0.12 | 0.08 | 0.15 |
| Crystal seed S silica alumina ratio | 38 | 91 | 42 |
| Product silica alumina ratio | 29 | 45 | 42 |
| Specific surface (m 2/g) | 262 | 342 | 316 |
| Pore volume (cm 3/g) | 0.26 | 0.33 | 0.31 |
| Mean pore size (nm) | 4.0 | 4.1 | 4.1 |
Table 1(continues) ZSM-48 Zeolite synthesis proportioning raw materials and product property.
| Each component relative proportion (mol ratio) | Embodiment 4 | Embodiment 5 |
| R/SiO 2 | 0.18 | 0.11 |
| SiO 2/Al 2O 3 | 33 | 35 |
| Na 2O/SiO 2 | 0.074 | 0.075 |
| H 2O/SiO 2 | 21.3 | 18.6 |
| Crystal seed S/SiO 2(mass ratio) | 0.3 | 0.18 |
| Crystal seed S silica alumina ratio | 105 | 102 |
| Product silica alumina ratio | 31 | 33 |
| Specific surface (m 2/g) | 292 | 285 |
| Pore volume (cm 3/g) | 0.28 | 0.26 |
| Mean pore size (nm) | 4.2 | 4.4 |
As can be seen from the table, the silica alumina ratio of ZSM-48 molecular sieve that synthesizes of the present invention is lower.
Claims (6)
1. a preparation method for low silica-alumina ratio ZSM-48 molecular sieve, is characterized in that comprising the steps:
(1) crystal seed S, template R, silicon source, aluminium source, sodium hydroxide and water are mixed preparation feedback mixture; Template R is 12-crown ether-4;
(2) reaction mixture step (1) prepared at 150 ~ 170 DEG C, hydrothermal crystallizing 4 ~ 8 days, crystallization product after filtration, washing, dry and roasting obtain low silica-alumina ratio ZSM-48 molecular sieve; The mixture that step (1) is prepared has following composition, with oxide basis mol ratio: R/SiO
2=0.08 ~ 0.18; SiO
2/ Al
2o
3=33 ~ 48; Na
2o/SiO
2=0.074 ~ 0.085; H
2o/SiO
2=16.5 ~ 21.3; S/SiO
2mass ratio is 0.08 ~ 0.3; Wherein SiO
2do not comprise the silicon-dioxide in crystal seed S, S is ZSM-48 molecular sieve; The described silicon oxide of low silica-alumina ratio ZSM-48 molecular sieve and the mol ratio of aluminum oxide are 29 ~ 45; Crystal seed ZSM-48 molecular sieve is the sodium form molecular sieve of roasting or the sodium form molecular sieve of non-roasting, and the mol ratio of silicon oxide and aluminum oxide is between 38 ~ 105.
2. in accordance with the method for claim 1, it is characterized in that: low silica-alumina ratio ZSM-48 molecular sieve specific surface is 262 ~ 342m
2/ g, pore volume is 0.26 ~ 0.33cm
3/ g, mean pore size is 4 ~ 4.4nm.
3. in accordance with the method for claim 1, it is characterized in that: the temperature of preparation feedback mixture is between 20 ~ 90 DEG C.
4. in accordance with the method for claim 1, it is characterized in that: the temperature of preparation feedback mixture is between 50 ~ 80 DEG C.
5. in accordance with the method for claim 1, it is characterized in that: silicon source is White Carbon black, aluminium source is sodium aluminate.
6. in accordance with the method for claim 1, it is characterized in that: Yao Lv source, silicon source adds after dissolving completely.
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| CN104003413B (en) * | 2014-05-27 | 2016-05-11 | 复旦大学 | A kind of preparation method of nano bar-shape ZSM-48 molecular sieve |
| CN110127719B (en) * | 2018-02-02 | 2022-08-19 | 华东理工大学 | Preparation method of ZSM-48 molecular sieve with low Si/Al ratio |
| CN110856819B (en) * | 2018-08-24 | 2022-07-26 | 国家能源投资集团有限责任公司 | Surface aluminum-rich molecular sieve, preparation method and application thereof, isomerization reaction catalyst and application thereof |
| CN111137905B (en) * | 2018-11-06 | 2022-03-22 | 国家能源投资集团有限责任公司 | ZSM-48 molecular sieve and preparation method thereof |
| CN113548675B (en) * | 2020-04-26 | 2023-03-10 | 中国石油化工股份有限公司 | ZSM-48 molecular sieve and preparation method thereof |
| CN113548676B (en) * | 2020-04-26 | 2022-11-15 | 中国石油化工股份有限公司 | Preparation method of hydrogen type silicon-aluminum ZSM-48 molecular sieve |
| CN113325042B (en) * | 2021-06-11 | 2022-11-15 | 吉林大学 | Sodium MTW molecular sieve, preparation method and application thereof, ammonia gas sensor, preparation method and application thereof |
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| CN1930083A (en) * | 2004-03-05 | 2007-03-14 | 埃克森美孚研究工程公司 | Synthesis of ZSM-48 crystals with heterostructural, non ZSM-48, seeding |
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| FR2917645B1 (en) * | 2007-06-20 | 2011-04-08 | Centre Nat Etd Spatiales | USE OF MODIFIED ZEOLITES FOR MOLECULAR DECONTAMINATION. |
| US8003074B2 (en) * | 2007-09-18 | 2011-08-23 | Exxonmobil Research And Engineering Company | Synthesis of high activity ZSM-48 |
| CN102040231B (en) * | 2011-01-14 | 2012-05-23 | 山西大同大学 | Method for synthesizing zeolite ZSM-48 |
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